CN111909570B - Synthesis method of silver nanowire ink and preparation method of flexible conductive film - Google Patents
Synthesis method of silver nanowire ink and preparation method of flexible conductive film Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002042 Silver nanowire Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001308 synthesis method Methods 0.000 title claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 74
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002244 precipitate Substances 0.000 claims abstract description 36
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 35
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 35
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 35
- 239000011259 mixed solution Substances 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 31
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 239000000835 fiber Substances 0.000 claims abstract description 24
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 22
- 239000004417 polycarbonate Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000012452 mother liquor Substances 0.000 claims abstract description 15
- 238000007639 printing Methods 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 238000007760 metering rod coating Methods 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002985 plastic film Substances 0.000 claims description 3
- 229920006255 plastic film Polymers 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 239000000976 ink Substances 0.000 description 75
- 239000010408 film Substances 0.000 description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000032798 delamination Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000011231 conductive filler Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- -1 or the like Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0547—Nanofibres or nanotubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention discloses a method for synthesizing silver nanowire printing ink, which is implemented according to the following steps: step 1, dissolving a certain amount of polycarbonate fiber, silver nitrate and polyvinylpyrrolidone (PVP) in an ethylene glycol solution, and then adding a ferric trichloride aqueous solution to obtain a mixed solution; step 2, magnetically stirring the mixed solution at 70 ℃ for 40min, after the color of the solution is changed into dark reddish brown, increasing the temperature to 160 ℃, and magnetically stirring at constant temperature for 80min to obtain mother liquor; step 3, centrifuging and cleaning the mother liquor obtained by the reaction in the step 2 for multiple times by using absolute ethyl alcohol to obtain a precipitate; and 4, dispersing the precipitate obtained in the step 3 in a solvent to obtain the silver nanowire ink. Solves the problem that the nano-silver conductive ink needs to be sintered and cured at high temperature after being coated in the prior art. The invention also discloses a preparation method of the flexible conductive film.
Description
Technical Field
The invention belongs to the technical field of ink preparation methods, relates to a synthetic method of silver nanowire ink, and also relates to a preparation method of a flexible conductive film.
Background
In the 21 st century, the internet technology is hot and trendy, and the mainstream electronic market demand is further deepened from the initial informatization development, so that the intelligent and personalized internet technology becomes intelligent and personalized. Under the rapid development momentum, flexible electronic (flexible electronic) rapidly rises, and the flexible electronic has wide application prospect and great market potential. According to the prediction of Maximize Market Research, the flexible electronic industry is expected to increase by about 11% from 2017 to 2026, the flexible electronic industry reaches 432 hundred million dollars in scale, and the application range of the flexible electronic industry is far beyond the fields of current sensors, displays, thin-film solar cells and the like. In the technical implementation method of the flexible Electronic device, the printed Electronic Technology (Print Electronic Technology) is different from the traditional photoetching process, so that the process Technology is simple and easy to operate, the efficiency is much higher, the process manufacturing cost is low, the requirement on the substrate is much lower, and the method has high industrial application value.
The key to the realization of printing technology lies in the development of conductive inks. Different from the traditional printing ink, the conductive filler with the conductive property endows the conductive ink with conductivity, so that the conductive ink can be applied to the fields of electronic devices such as sensors, displays, radio frequency tags and the like. Conductive inks can be classified into inorganic conductive inks and organic conductive inks according to the nature of the conductive filler. The organic conductive ink is inferior in conductivity and printability and used in a small amount. Inorganic inks can be further classified into carbon-based and nano-metal-based conductive inks. In carbon-based inks, graphite and carbon black are commonly used as conductive fillers to prepare conventional carbon-based inks. The ink has low price but poor conductivity. With the development of material science, carbon-based ink conductive fillers which are researched, popularized and applied more are carbon fibers and carbon nanotube nano metal-based conductive ink which mainly takes gold (Au), copper (Cu) and silver (Ag) as conductive units. Au is excellent in conductivity, but is expensive. In contrast, cu is high in cost performance, but poor in oxidation resistance. In sum, ag has far better electrical conductivity than other metals, excellent thermal conductivity and moderate price, and thus is a hot material in recent conductive ink research.
The properties of the silver-based conductive ink are key factors for determining the conductive performance of the conductive film. Therefore, the proportion relation between the conductive filler and other components in the ink is adjusted, so that the properties of the ink, such as viscosity, stability, printability and the like, are adjusted, and finally the ink keeps excellent conductive performance and has better cost performance and market competitiveness. After being coated, the common nano silver conductive ink needs to be sintered and solidified at a high temperature of more than 400 ℃ to form a conductive path between silver nanowires, so that the thin film of the conductive ink can be conductive. The high temperature resistance of the film substrate puts high requirements on the high temperature resistance, so that the application of the nano-silver conductive ink is limited. Therefore, how to reduce the sintering curing temperature of the nano silver conductive ink is one of the hot research spots of the silver conductive ink at present.
In addition, factors such as the coating mode, the drying form, the curing parameters, the type of the base material and the like of the ink can cause the physical and chemical properties such as the conductivity, the bending resistance, the wear resistance and the like of the film to change, and further influence the service performance and the service life of electronic components. Therefore, the discussion of the film forming process of the ink is a key point for further improving the application value of the ink.
Disclosure of Invention
The invention aims to provide a method for synthesizing silver nanowire printing ink, which solves the problem that the nano silver conductive printing ink needs to be sintered and solidified at high temperature after being coated in the prior art.
The invention also aims to provide a preparation method of the flexible conductive film.
The technical scheme adopted by the invention is that the synthesis method of the silver nanowire printing ink is implemented according to the following steps:
step 1, dissolving a certain amount of polycarbonate fiber, silver nitrate and polyvinylpyrrolidone (PVP) in an ethylene glycol solution, and then adding a ferric trichloride aqueous solution to obtain a mixed solution;
step 2, magnetically stirring the mixed solution at 50-90 ℃ for 30-60 min, after the color of the solution is changed into dark reddish brown, increasing the temperature to 140-180 ℃, and magnetically stirring at constant temperature for 60-100 min to obtain mother liquor;
step 3, centrifuging and cleaning the mother liquor obtained in the step 2 for multiple times by using absolute ethyl alcohol to obtain a precipitate;
and 4, dispersing the precipitate obtained in the step 3 in a solvent to obtain the silver nanowire ink.
The first technical means of the present invention is also characterized in that,
the mixed solution in the step 1 comprises the following components in percentage by mass: 0.02-1% of polycarbonate fiber, 1-5% of silver nitrate, 1-5% of polyvinylpyrrolidone (PVP), 1-7% of ferric trichloride aqueous solution and 82-96.98% of ethylene glycol, wherein the sum of the mass percentages of the components is 100%.
The mass concentration of the ferric trichloride aqueous solution is 1 multiplied by 10 -5 ～5×10 -4 g/mL。
The solvent is one of ethanol, ethylene glycol, polyethylene glycol, polyvinyl alcohol, triethanolamine, and glycerol.
The mass concentration of the silver nanowire printing ink prepared in the step 4 is 0.1 g/mL-1 g/mL.
The second technical scheme adopted by the invention is that the preparation method of the flexible conductive film is implemented according to the following steps:
step (1), uniformly coating the silver nanowire ink prepared by the synthesis method of the silver nanowire ink on a substrate, and drying at room temperature to obtain a conductive film A;
and (2) placing the conductive film A in a constant-temperature drying oven for drying and curing to obtain the flexible conductive film.
The coating method is printing, wire bar coating or Meyer bar coating, and the substrate is paper or plastic film.
The thickness of the silver nanowire conductive ink layer in the conductive film A is 1 multiplied by 10 -7 ～1×10 -6 m, sheet resistance of 1 × 10 -6 Ω·cm～1×10 -4 Ω·cm。
In the step (2), the drying, curing and curing temperature is 150-300 ℃ in a constant-temperature drying oven, and the curing time is 30-120 min.
The sheet resistance of the flexible conductive film finally obtained in the step (2) is 1 multiplied by 10 -7 Ω·cm～1×10 -6 Ω·cm。
The invention has the beneficial effects that:
according to the invention, the polycarbonate fiber is added, so that silver atoms are selectively deposited on the fiber template and are induced to directionally grow into the silver nanowires, and thus the prepared silver nanowire ink has excellent conductivity. And by adding different solvents, the silver nanowires and the fiber compound thereof are stably dispersed in the ink and can be cured at low temperature. And finally, the conductive film obtained by the ink has the optimal conductivity by using a proper coating mode, curing temperature, curing time and printing base material.
Drawings
FIG. 1 is a schematic view of a conductive film prepared in example 3 in a method for preparing a flexible conductive film according to the present invention;
fig. 2 is a schematic view of the conductive film prepared in example 4 in the method for preparing a flexible conductive film according to the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a synthesis method of silver nanowire printing ink, which is implemented according to the following steps:
step 1, dissolving a certain amount of polycarbonate fiber, silver nitrate and polyvinylpyrrolidone (PVP) in an ethylene glycol solution, and then adding an iron trichloride aqueous solution to obtain a mixed solution, wherein the mixed solution comprises the following components in percentage by mass: 0.02-1% of polycarbonate fiber, 1-5% of silver nitrate, 1-5% of polyvinylpyrrolidone (PVP), 1-7% of ferric trichloride aqueous solution and 82-96.98% of ethylene glycol, wherein the sum of the mass percentages of the components is 100%; the mass concentration of the ferric trichloride aqueous solution is 1 multiplied by 10 -5 ～5×10 -4 g/mL；
Step 2, magnetically stirring the mixed solution at 50-90 ℃ for 30-60 min, after the color of the solution is changed into dark reddish brown, increasing the temperature to 140-180 ℃, and magnetically stirring at constant temperature for 60-100 min to obtain mother liquor;
step 3, centrifuging and cleaning the mother liquor obtained in the step 2 for multiple times by using absolute ethyl alcohol to obtain a precipitate;
and 4, dispersing the precipitate obtained in the step 3 in a solvent, wherein the solvent is one of ethanol, glycol, polyethylene glycol, polyvinyl alcohol, triethanolamine and glycerol, so as to obtain the silver nanowire ink, and the mass concentration of the obtained silver nanowire ink is 0.1 g/mL-1 g/mL.
The invention relates to a preparation method of a flexible conductive film, which is implemented according to the following steps:
step (1), uniformly coating the silver nanowire ink prepared by the synthesis method of the silver nanowire ink on a substrate, and drying at room temperature to obtain a conductive film A; the thickness of the silver nanowire conductive ink layer in the conductive film A is 1 multiplied by 10 -7 ～1×10 -6 m, sheet resistance of 1 × 10 -6 Ω·cm～1×10 -4 Ω · cm, wherein the mode of coating is printing such as offset printing, inkjet printing, screen printing, or the like, or wire bar coating method or meyer bar coating method, and the substrate is paper such as coated paper, offset paper, or the like, or plastic film such as Polyester (PET) film, polyethylene (PE) film, or the like;
step (2), the conductive film A is placed in a constant-temperature drying oven for drying and curing, the curing temperature is 150-300 ℃, the curing time is 30-120 min, and the flexible conductive film is obtained, wherein the sheet resistance is 1 multiplied by 10 -7 Ω·cm～1×10 -6 Ω·cm。
Example 1
Dissolving polycarbonate fiber, silver nitrate and polyvinylpyrrolidone PVP in ethylene glycol solution, and adding into the solution with mass concentration of 8 × 10 -5 Forming a mixed solution by using a g/mL ferric trichloride aqueous solution, wherein the mixed solution contains 0.02% of polycarbonate fiber by mass, 1.5% of silver nitrate by mass, 2% of PVP by mass, 2% of ferric trichloride aqueous solution by mass and 94.48% of ethylene glycol by mass; magnetically stirring the mixed solution at 50 deg.C for 60min, adjusting the temperature to 140 deg.C after the solution color becomes dark reddish brown, and magnetically stirring at constant temperature for 100min. After the reaction is finished, centrifuging and cleaning mother liquor obtained by the reaction for multiple times by using absolute ethyl alcohol to obtain a precipitate;
and (3) dispersing 0.22g of the precipitate in 1mL of absolute ethyl alcohol to ensure that the mass concentration of the precipitate is 0.22g/mL, shaking up the precipitate to obtain the silver nanowire conductive ink, and standing the ink for 17 days without visible layering. Spin coating 0.1mL of the ink on 150g coated paper to obtain a thickness of 3X 10 -7 m of conductive ink layers. Resistivity of 1X 10 after drying at room temperature -5 Omega cm. Is connected withThen the film is placed in a constant temperature drying oven, dried and solidified for 30min at the temperature of 150 ℃ to obtain the conductive film, and the resistivity of the film is 1 multiplied by 10 -6 Ω·cm。
Example 2
Dissolving polycarbonate fiber, silver nitrate and polyvinylpyrrolidone (PVP) in ethylene glycol solution, and adding into the solution with mass concentration of 1 × 10 -5 Forming a mixed solution by using a g/mL ferric trichloride aqueous solution, wherein in the mixed solution, the mass fraction of the polycarbonate fiber is 0.06%, the mass fraction of the silver nitrate is 1%, the mass fraction of the PVP is 1%, the mass fraction of the ferric trichloride aqueous solution is 1%, and the mass fraction of the ethylene glycol is 96.94%; magnetically stirring the mixed solution at 60 deg.C for 50min, adjusting the temperature to 160 deg.C after the solution color becomes dark reddish brown, and magnetically stirring at constant temperature for 90min. After the reaction is finished, centrifuging and cleaning mother liquor obtained by the reaction for multiple times by using absolute ethyl alcohol to obtain a precipitate;
and (3) dispersing 0.44g of the precipitate in 3mL of absolute ethyl alcohol to ensure that the mass concentration of the precipitate is 0.15g/mL, and shaking up the precipitate to obtain the silver nanowire conductive ink. The ink was allowed to stand for 15 days without visible delamination. The ink was ink-jet printed on 150g coated paper to obtain a size of 20X 20mm and a thickness of 1X 10 -7 m, conductive ink layer. The film was dried at room temperature and the resistivity was measured to be 1X 10 -4 Omega cm. Then the film is placed in a constant temperature drying oven, dried and cured for 30min at 180 ℃ to obtain the conductive film, and the resistivity of the film is 1 multiplied by 10 -6 Ω·cm。
Example 3
Dissolving polycarbonate fiber, silver nitrate and polyvinylpyrrolidone (PVP) in ethylene glycol solution, and adding into the solution with mass concentration of 8 × 10 -5 Forming a mixed solution by using a g/mL ferric trichloride aqueous solution, wherein in the mixed solution, the mass fraction of the polycarbonate fiber is 0.08%, the mass fraction of the silver nitrate is 1.22%, the mass fraction of the PVP is 1.71%, the mass fraction of the ferric trichloride aqueous solution is 1.95%, and the mass fraction of the ethylene glycol is 95.04%; magnetically stirring the mixed solution at 70 deg.C for 40min, adjusting the temperature to 160 deg.C after the solution color turns to dark reddish brown, and magnetically stirring at constant temperature for 80min. After the reaction is finished, the mother liquor obtained by the reaction is used as anhydrous ethyl acetateCentrifuging and cleaning with alcohol for multiple times to obtain precipitate;
and (3) dispersing 0.88g of the precipitate in 1mL of absolute ethyl alcohol to ensure that the mass concentration of the precipitate is 0.88g/mL, and shaking up the precipitate to obtain the silver nanowire conductive ink. The ink was allowed to stand for 20 days without visible delamination. Sucking 0.1mL of the solution with a suction tube, and dropping the solution on 150g of coated paper to obtain a coated paper with a size of 20X 20mm and a thickness of 5X 10 -7 m of conductive ink layers. Resistivity measured after drying at room temperature was 5X 10 -6 Omega cm. Then, the film was placed in a constant temperature drying oven, dried and cured at 200 ℃ for 1 hour to obtain a conductive film, as shown in FIG. 1, having a resistivity of 1X 10 -7 Ω·cm。
Example 4
Dissolving polycarbonate fiber, silver nitrate and polyvinylpyrrolidone (PVP) in ethylene glycol solution, and adding into the solution with mass concentration of 1 × 10 -4 Forming a mixed solution by using a g/mL ferric trichloride aqueous solution, wherein the mixed solution contains 1% of polycarbonate fiber by mass, 3% of silver nitrate by mass, 3.5% of PVP by mass, 7% of ferric trichloride aqueous solution by mass and 85.5% of ethylene glycol by mass; magnetically stirring the mixed solution at 70 deg.C for 40min, adjusting the temperature to 180 deg.C after the solution color turns to dark reddish brown, and magnetically stirring at constant temperature for 90min. After the reaction is finished, centrifuging and cleaning mother liquor obtained by the reaction for multiple times by using absolute ethyl alcohol to obtain a precipitate;
and (3) dispersing 0.22g of the precipitate in 2mL of ethylene glycol to ensure that the mass concentration of the precipitate is 0.11g/mL, and shaking up the precipitate to obtain the silver nanowire conductive ink. The ink was allowed to stand for 30 days without visible delamination. The ink was applied to a PE film by a Meyer bar coating method to give a thickness of 1X 10 -7 m, conductive ink layer. Then, the film was dried and cured in a constant temperature oven at 200 ℃ for 1 hour to obtain a conductive film, as shown in FIG. 2, having a resistivity of 5X 10 -6 Ω·cm。
Example 5
Dissolving polycarbonate fiber, silver nitrate and polyvinylpyrrolidone PVP in ethylene glycol solution, and adding 1 × 10 mass concentration -5 g/mL of ferric trichloride aqueous solution to form a mixed solution, wherein the mixed solutionIn the preparation method, the mass fraction of the polycarbonate fiber is 0.1%, the mass fraction of the silver nitrate is 5%, the mass fraction of the PVP is 5%, the mass fraction of the ferric trichloride aqueous solution is 5%, and the mass fraction of the ethylene glycol is 84.9%; magnetically stirring the mixed solution at 90 deg.C for 45min, adjusting the temperature to 180 deg.C after the solution color turns to dark reddish brown, and magnetically stirring at constant temperature for 75min. After the reaction is finished, centrifuging and cleaning mother liquor obtained by the reaction for multiple times by using absolute ethyl alcohol to obtain a precipitate;
and 2.2g of the precipitate is taken and dispersed in 5mL of glycerol to ensure that the mass concentration of the precipitate is 0.44g/mL, and the precipitate is shaken and shaken uniformly to obtain the silver nanowire conductive ink. The ink was allowed to stand for 50 days without visible delamination. The ink was screen printed onto a PET film to a thickness of 7X 10 -6 m of conductive ink layers. Then the film is placed in a constant temperature drying oven, dried and solidified for 30min at 300 ℃ to obtain the conductive film, and the resistivity of the film is 3 multiplied by 10 -7 Ω·cm。
Example 6
Dissolving polycarbonate fiber, silver nitrate and polyvinylpyrrolidone PVP in ethylene glycol solution, and adding 3 × 10 mass concentration -4 Forming a mixed solution by using a g/mL ferric trichloride aqueous solution, wherein in the mixed solution, the mass fraction of the polycarbonate fiber is 0.04%, the mass fraction of the silver nitrate is 1.5%, the mass fraction of the PVP is 2%, the mass fraction of the ferric trichloride aqueous solution is 2%, and the mass fraction of the ethylene glycol is 94.46%; magnetically stirring the mixed solution at 70 deg.C for 30min, adjusting the temperature to 160 deg.C after the solution color turns to dark reddish brown, and magnetically stirring at constant temperature for 85min. After the reaction is finished, centrifuging and cleaning mother liquor obtained by the reaction for multiple times by using absolute ethyl alcohol to obtain a precipitate;
and (3) dispersing 0.66g of the precipitate in 2mL of polyvinyl alcohol to ensure that the mass concentration of the precipitate is 0.33g/mL, and shaking up the precipitate to obtain the silver nanowire conductive ink. The ink was allowed to stand for 34 days without visible delamination. Sucking 0.1mL of the solution with a pipette and dropping the solution on a 150g PET film to obtain a film having a size of 20X 20mm and a thickness of 3X 10 -7 m of conductive ink layers. Then the film is placed in a constant temperature drying oven, dried and cured for 80min at 270 ℃ to obtain the conductive film, and the resistivity of the film is 8 multiplied by 10 -7 Ω·cm。
Example 7
Dissolving polycarbonate fiber, silver nitrate and polyvinylpyrrolidone (PVP) in ethylene glycol solution, and adding into the solution with mass concentration of 8 × 10 -5 ～5×10 -4 Forming a mixed solution by using a g/mL ferric trichloride aqueous solution, wherein in the mixed solution, the mass fraction of the polycarbonate fiber is 0.08%, the mass fraction of the silver nitrate is 2.5%, the mass fraction of the PVP is 5%, the mass fraction of the ferric trichloride aqueous solution is 3%, and the mass fraction of the ethylene glycol is 89.42%; magnetically stirring the mixed solution at 90 deg.C for 35min, adjusting the temperature to 149 deg.C after the solution color turns to dark reddish brown, and magnetically stirring at constant temperature for 100min. After the reaction is finished, centrifuging and cleaning the mother liquor obtained by the reaction for multiple times by using absolute ethyl alcohol to obtain a precipitate;
and (3) dispersing 0.22g of the precipitate in 1mL of polyethylene glycol to ensure that the mass concentration of the precipitate is 0.22g/mL, and shaking up the precipitate to obtain the silver nanowire conductive ink. The ink was left to stand for 32 days without visible delamination. Sucking 0.1mL of the ink with a pipette, and dropping the ink on a Polyethylene (PE) film to obtain a film having a size of 20X 20mm and a thickness of 1X 10 -7 m of conductive ink layers. Then the film is placed in a constant temperature drying oven, dried and cured for 80min at 270 ℃ to obtain the conductive film, and the resistivity of the film is 2.5 multiplied by 10 -7 Ω·cm。
Claims (9)
1. A synthesis method of silver nanowire ink is characterized by comprising the following steps:
step 1, dissolving a certain amount of polycarbonate fiber, silver nitrate and polyvinylpyrrolidone (PVP) in an ethylene glycol solution, and then adding an iron trichloride aqueous solution to obtain a mixed solution;
step 2, magnetically stirring the mixed solution at 50-90 ℃ for 30-60 min, after the color of the solution is changed into dark reddish brown, increasing the temperature to 140-180 ℃, and magnetically stirring at constant temperature for 60-100 min to obtain mother liquor;
step 3, centrifuging and cleaning the mother liquor obtained in the step 2 for multiple times by using absolute ethyl alcohol to obtain a precipitate;
step 4, dispersing the precipitate obtained in the step 3 in a solvent to obtain silver nanowire ink;
the mixed solution in the step 1 comprises the following components in percentage by mass: 0.02-1% of polycarbonate fiber, 1-5% of silver nitrate, 1-5% of polyvinylpyrrolidone PVP, 1-7% of ferric trichloride aqueous solution and 82-96.98% of ethylene glycol, wherein the sum of the mass percentages of the components is 100%.
2. The method for synthesizing the silver nanowire ink as claimed in claim 1, wherein the mass concentration of the ferric trichloride aqueous solution is 1 x 10 -5 ～5×10 -4 g/mL。
3. The method for synthesizing silver nanowire ink according to claim 1, wherein the solvent is one of ethanol, ethylene glycol, polyethylene glycol, polyvinyl alcohol, triethanolamine and glycerol.
4. The method for synthesizing the silver nanowire ink as claimed in claim 1, wherein the mass concentration of the silver nanowire ink prepared in the step 4 is 0.1 g/mL-1 g/mL.
5. The preparation method of the flexible conductive film is characterized by comprising the following steps:
uniformly coating the silver nanowire ink prepared in the claim 2 on a substrate, and drying at room temperature to obtain a conductive film A;
and (2) placing the conductive film A in a constant-temperature drying box for drying and curing to obtain the flexible conductive film.
6. The method as claimed in claim 5, wherein the coating is performed by printing or wire bar coating or Meyer bar coating, and the substrate is paper or plastic film.
7. The method for preparing a flexible conductive film according to claim 5Characterized in that the thickness of the silver nanowire conductive ink layer in the conductive film A is 1 multiplied by 10 -7 ～1×10 -6 m, sheet resistance of 1X 10 -6 Ω·cm～1×10 -4 Ω·cm。
8. The method for preparing a flexible conductive film according to claim 5, wherein in the step (2), the drying curing temperature in the constant-temperature drying oven is 150 ℃ to 300 ℃, and the curing time is 30min to 120min.
9. The method as claimed in claim 5, wherein the sheet resistance of the flexible conductive film obtained in step (2) is 1 x 10 -7 Ω·cm～1×10 -6 Ω·cm。
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